Corrosion control in condensing systems



June 27, 1961 J. T. CABBAGE coRRosloN CONTROL 1N coNDENsING SYSTEMS Filed sept. 17, 195s hydrogenation eifluent and recycled thereto.

nited States Patent() 2,990,431 CORROSION CGNTROL 'IN CONDENSING SYSTEMS `lohn T.' Cabbage, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware Filed Sept. 17, 1958, Ser. No. 761,527 9 Claims. (Cl. 260-667) This invention relates to elimination of corrosion. In one of its aspects, it relates to the handling of a conversion euent containing acid generating or acidic substances which, when in contact with liquid water, cause corrosion of apparatus containing said effluent, the said handling comprising maintaining said eluent above the dew point of water under the conditions under which it is passed to a point of neutralization and then cooling said eiiiuent to a temperature at which elective neutralization takes place just prior to contacting said etliuent with a neutralizing agent. In another of its aspects, the invention relates to the prevention of corrosion by hydrogen chloride in a system such as a hydrogenation system by maintaining the vapor effluent at a temperature above the dew point of water until just before the effluent is contacted with a neutralizing agent and a stream of cooled, treated liquid eflluent. In a more specific aspect of the invention, corrosion is prevented in a system in which a catalytic hydrogenation process efuent is neutralized to eliminate hydrogen chloride therefrom which is contained therein due to conversion during hydrogenation of organic chlorides in the original feed which comprises maintaining said effluent above the dew point of water, admixing said elfluent with earlier neutralized eluent just prior to neutralization to reduce its temperature to one at which effective neutralization can occur in a desirable manner without vaporization of neutralizing agent and then neutralizing said eiuent with said agent. In a specific embodiment of the invention, corrosion in the system by hydrogen chloride produced from organic chlorides in the feed to a catalytic hydrogenation process, or from chlorides on the catalyst, is prevented by maintaining the effluent from the hydrogenation process above the dew point of water, e.g., about 225 F., to prevent water condensation and then adding a stream of cooled liquid hydrocarbon which can be a stream which has been previously treated, as here described, following which the now cooled effluent is immediately contacted with a solution of caustic alkali.

It is known to inject alkali into various conversion eluents to prevent corrosion of equipment by acid generating or acidic substances in the eluent when said effluent is cooled to, or below, the dew point of water. However, contact with ammonia gas and other like materials leaves ammonia or other of said materials in the recycle hydrogen which, as it is known, is usually recovered from the It is also known that ammonia is not desirable in the recycle hydrogen "due to its deactivating effect on the catalyst. Therefore, a non-volatile neutralizing agent, such as caustic or caustic soda, in an aqueous solution is ordinarily used. If the temperature is kept above the dew point of water until the neutralizing agent is added, there results evaporation of water from the neutralization agent composition with consequent plugging of the equipment with dry caustic or caustic soda downstream of the point of injection thereof. I have now conceived that just prior to or simultaneously with the injection of the caustic solution or other equivalent solution into contact with the effluent, there should be also introduced a coolant which can be a recycle stream of treated hydrogenation eiuent, thus to reduce the temperature of the admixture of neutralizing agent and eiuent, avoiding evaporation of water from neutralizing agent and its carry-over and deposition in the equipment.

ICC

. l2 .It is an object of this invention to provide .method and means for the elimination ofcorrosion. It is another object of this invention to provide method and means for the elimination ofcorrosion caused by the .cooling and consequent condensation of acid or acid-forming materials and waterin equipment in which an ethuent containing said acid or acid-forming material' and waterfvapor is neu; tralized. It is another object of this invention to neutralize a hydrocarbon hydrogenation efuent which contains acid or acid-forming materials and .water vapor Without corrosion of the apparatus containing said efuent just prior to its neutralization. Other aspects, objects and the several advantages of this invention are apparent from a consideration of this disclosure, the drawing and the'appended claims.

According to the present invention, there are provided a. method and apparatus for substantially eliminating cor.- rosion of equipment used to process an eiue'nt which, as produced, is above the dew'point of water in the equipment under the conditions-prevailing upon its production and which contains acid 'generating or acidic material which, when in contact with liquid water, causes corrosion of apparatus containing the same and which eluent is neutralized in the ensuing treatment, the method compris-r ing maintaining said efuent above the dew point of water in theY equipment under the conditions prevailing upon said efliuent, and contacting the eiuent with a neutralizing agent under conditions below the dew point of water.

The method of the invention is lparticularly adapted to the prevention of corrosion by hydrogen chloride produced from organic chlorides in a feed to a catalytic hydrogenation process or fromchlorides on'the hydrogenation catalyst used in such a process when the efuent from such a process is being conveyed to or is at point at which neutralization is to be accomplished. v

When water is present in the system or carried in by the -fced or produced in the reaction in such a process or equivalent process, the reactor efliuent becomes very corrosive as soon as it is cooled to the dew point of water and actu-ally corrosion will take place even ybefore the'average temperature is reduced to the dew point of water because water condensation occurs on cold surfaces such as condenser tube walls 4and pipe walls. Thus, the hydrogen chloride or other acid-forming material dissolves in any liquid water -in the system causing corrosion. This hydrogen chloride can, of course, be easily neutralized byinjecting ammonia gas but such a step would leave 'ammonia in the efiiuent and/ or in the recycle hydrogen when such hydrogen is involved `and further, since ammonia deac.- tivates many catalysts, especially many of those utilized in hydrogenation, the use of ammonia is desirably avoided; Indeed, the use of most any volatile neutralizing agentis to be avoided and use'made of a non-volatile neutralizing agent. In any event, the agent is preferably non-volatile under the conditions of neutralization and caustic solution is considered to meet the requirements. However, caustic solution can not be used at elevated temperatures, that is, temperatures above the deW point of Water because the evaporation of water causes concentration and crystallization of the caustic with the consequent plugging of equipment with dry caustic. y

The problem which this invention solves then is the control of corrison up to the locus of contact of neutralizing yagent with the reactor eluent at which locus, of course, the corrosion elfect of the hydrogenchloride or other corrosive material is negated.

In the case of a hydrogenation etuent from a process in which a hydrocarbon is hydrogenalted under conditions producing an eiuent containing hydrogen chloride and water, the eluent from the reactor is cooled to a teniperature which is still sufficiently high to prevent water i condensation, in this instance approximately 220 F.

embodiment.

The itemperature of the eiuent maintained at this level l `until-the Iaqueous neutralizing vagenti-is added kdirectly .to

the reactor eiiluent at this temperature. There is also added to the eliluent a stream of cool liquid hydrocarbon -whichhasearlierjbeen treated according to the invention, -tlius'yirtually simultaneously r.cooling the eiuent 'below the dewipoint of vwaiter therein andneutralizing'harmful acidic ksubstances therein, vsubstantially completely avoiding corrosion ofthele'qui-pment. Although itis not Vabsolutely necessary :that the-'cooled liquid lhydrocarbon be added to the eluen-t at :precisely the instant the `efiluent is .to be neutralized, in the now preferred form of iiheinv'ention,u the cooling by treated effluent or other means Vpreferably is practiced substantially simultaneously with ithe neutralization, :thus'obtaining maximum benefit of the invention. The temperature of the cooling agent lor cooling means-selected -should be such that upon addition of thezneutralizing agent or solution, there will occur no substantial dehydration and crystallization of the neutralizing agent, thus `avoiding carry-over of caustic or other material undesired downstream in the apparatus.

.By .use of the method of the invention, the usual' requirements of expensive'alloy heat exchangers and ancillary equipment ordinarily used to bring down the reactor eluent vtemperature to caustic washing temperatures are completely avoided.

` It :is within the scope of the present invention Ato operaterall steps with automatic controls.

v.Referring now to the drawing, in FIGURE 1 there is shown diagrammatically Ythe treatment of an etlluent from -ahydrogenation reactor, not shown, employing the varioussteps ofthe invention as it is Iembodied in a .specific FIGURE 2 shows in cross-section, construction of a pipe containing a heating element and outer insulation suitable for conveyingrthe effluent from a preliminarycooler to `the `point at which the eliiuent is admixed withv neutralizing agent, as more fully described below.

Referring now to FIGURE V1, hydrogenation effluent 'froma'ireacton not shown, Ain which reactor an aromatic hydrocarbon is hydrogenated lto convert the same to a Vrnoredesirable product, .is passed lby way of pipe 1 at a temperatureof V500 cF. linto heat exchanger 2 wherein it is heat-interchanged with fresh feed, recycle hydrocarbon and hydrogen which enters the heat exchanger by way ofpipe 3 and is passed to the reactor by way of pipe 4. .Cooledhydrogenation eiuent at a temperature of 250 F. passes by pipe 5 through air lin cooler 6, leaving the cooleribyway of pipe 7 at a temperature of 220 F. There is-introduced by wayof pipe 8 into pipe 7, treated liquid hydrocarbon ata temperature' of 100 F. or slightly lower andi-there is also introduced by way of pipe 9 into pipe 7, caustic treating solution resulting in a nal admixture in pipefl'tl'havingatemperature of approximately 200 F. This'admixture is discharged into caustic contacting zone 11 :wherein neutralization is completed and fromwhich no `-asppreciate caustic is carried'over through pipe 12 which conveys the treated hydrogenation eiiiuent into high temperature separation zone 13. Caustic from zone 11 is by way of pump 1K4 and pipe 9 .to pipe 7. Thoughnot shown, itis within the scope of the invention :to :periodically or continuously remove a portion of the caustic from zone `11 Vand to replace it with #fresh treatingagent or solution. From high temperature separation zone 13, which is operated at a temperature of 200 F. and about V400 pounds per square inch gage, gases 'including ihydrogen,.which is recycled, are taken 'ot by'way Y.of pipe V15, Ycooler 16 and passed by way of pipe 17 into low .temperature separation zone 18. The temperature in this zone-is about `l00 F. and thepres- 'sureis 380 pounds per Asquare inch gage. Recycled hydrogen gas vis passed 4byzway of pipe 19-.to pipe 3 and from-.therezby -way of heat exchanger!` and pipe 4 to -the-'ireacton ydrogenatedhvdrocarbonrproduct is drawn oit from zone 13 by way of pipe 20. Also, liquid hydrocarbon from whichgaseshave been separated -inzone 18 -is passed by way of pipe 22, pump 23 and pipe 8 to pipe 7 for use as earlier described. Excess liquid hydrocarbon removed 'from zone 11S is Ipassed by pipe Z4 to pipe 20 for removal as .product ReferringY now toFIGURE 2, which is across-sectional view of pipe 7, the pipe wall is surrounded by a heating element 26 and insulation 27. .A temperaturerecorder controller sensing the temperature `of the euent in pipe 7 is used to control the yflow of electricity to the heating element. It is within the scope of the invention to use other means for heating the efuent in pipe 7 such las 'hot water pipe, etc., as will be understood by one skilled in the art in possession of this disclosure.

Following is a specilo operation in accordance `with this invention showing the reactor total charge, reactor effluent, caustic injection, and hydrocarbon injection, etc.:

' 1 Contains water vapor land hydrogen chloride vapor.

Caustic injection (19) Rate, gallon per hour 2,500 Concentration, B 25 Temperature, F. 200

Recycle hydrocarbon(8):

Rate, gallons per hour 500 Temperature, F. 100

Product Yield (20):

Pentane and lighter No. mols per hour-- 12.8 Dimethylcyclopentane do 27. l Cyclohexane do 8.7 Normal hexane do 34.3 Isohexane do- A17.1

Total 100.0

The total charge material passes over a nickel catalyst A(finely divided nickel on kieselguhr) in the reaction zone (not shown). Such zone operates at 40G-450 F. and at about -450-50() p.s.i.g., as `is known in the art, to'produce a saturated hydrocarbon eilluent. This eilluent is treated in accordance with this invention, said effluent containing water vapor and hydrogen chloride, with substantially no corrosion of the system.

Reasonable variation and modiiication are possible .within the scope of the foregoing disclosure, drawing and the appended claims to the invention, the essence of which is that there have been provided a method yand means for cooling and neutralizing an etlluent `such as a conversion `eliluent, more particularly a hydrogenation effluent, by maintaining said .eiuent above Ithe dew point of water in the system until just about the time when the neutralizing agent is added, thus accomplishing the cooling of the eiuent to an effective neutralizing temperature without corrosion and without carry-over of the neutralizing agent undesirably into the neutralized eluent stream.

I claim:

1. A method lfonsubstantially eliminating corrosion of equipment used to process an effluent stream which, as produced, is above the dew point of water in the equipment under the conditions prevailing upon its production and which contains acid generating or acidic material, which in contact with liquid water, causes corrosion of apparatus containing the eflluent stream and which effluent stream is neutralized in ensuing treatment and wherein the neutralizing agent will be crystallized and undesirably plug equipment unless neutralization is effected at a temperature at or below the dew point of water, the steps which comprise maintaining said eiuent stream above the dew point of water in the equipment under the conditions prevailing upon said efuent stream and then admixing with said `efluent stream a neutralizing agent under conditions below the dew point of water and such as to maintain water as a liquid in presence of said agent.

2. A method according to claim 1 wherein the eiuent is contacted with a coolant just about the time it is neutralized.

3. A method according to claim 1 wherein the neutralizing agent is caustic solution containing water and wherein just prior to introducing said solution, -a cool stream of efuent which has been treated as in said claim is added to the eiuent to bring its temperature down to a temperature at which crystallization of caustic, due to evaporation of water, is avoided.

4. A method according to claim l wherein `a hydrogenation hydrocarbon effluent containing hydrogen chloride is maintained above the dew point of water therein until there is added to said eluent a coolant adapted to bring the efuent down to a temperature below the dew point of water and substantially simultaneously therewith a caustic neutralizing solution containing water.

5. A method for the neutralization of an acid stream of a hot hydrocarbon hydrogenation efliuent which comprises cooling said stream of eilluent to a temperature just above the boiling point of water contained in said eiuent, then cooling said stream of eiuent to a temperature just below the dew point of said water forming liquid water in said stream of eiliuent, substantially simultaneously with said last-mentioned cooling injecting into said stream of eiluent a water solution of a non-volatile neutralizing agent, passing said stream of eiluent and injected agent to a neutralizing zone, in said zone, providing residence time for the completion of the neutralization, separating the now-used solution of neutralizing agent from the now-neutralized eiiuent, and recovering and further processing said eiiuent.

6. A method of handling and treating a hot conversion euent which contains water vapor and a substance which in the presence of liquid water will cause corrosion of the handling and treating equipment employed which comprises cooling said effluent to a temperature a few degrees above the dew point of the water vapor therein, then cooling said effluent to a temperature `a few degrees below the dew point of water in said effluent suicient to generate liquid water in said eluent, immediately admixing with said thus-cooled eiiluent a solution of a neutralizing agent in water, and recovering `from `said thus-treated eflluent, noncorrosive eiuent and said solution of said neutralizing agent.

7. A method according to claim 6 wherein the effluent upon admixture with the solution of said neutralizing agent is passed to -a separation zone wherein said solution of neutralizing agent is separated therefrom, the efuent now free of said agent is then passed to an elevated temperature separation zone where the etlluent free of neutralizing agent is further processed for separation into its component.

8. A method of handling and treating a hot conversion efuent which contains water vapor and a substance which in the presence of liquid water will cause corrosion of the handling and treating equipment employed which comprises cooling said `effluent to a temperature just above the dew point of the water vapor therein, then substantially simultaneously injecting into said effluent a cooling medium at a temperature and in a quantity suiicient to generate liquid water in said eliuent by cooling the same to a temperature a few degrees below its dew point and a solution of a non-volatile neutralizing agent, thus essentially simultaneously forming water in said eiuent at the time when it is being neutralized, recovering from said euent the injected and now-used solution of neutralizing agent )and then further processing said eluent.

9. A method for the neutralization of a lthydrogenation eluent containing water vapor and hydrogen chloride which will corrode the equipment in which the eluent is processed when liquid water is present and which efuent will cause' plugging of the equipment if neutralization is practiced upon said eluent at a temperature above the dew point of water due to the evaporation of liquid water from the neutralization agent used, depositing neutralization agent and, in some cases, a product of said neutralization, the improvement which comprises maintaining said eflluent above the dew point of water at a temperature of about 225 F. until just about the point of neutralization is reached, then cooling said effluent to a temperature below the dew point of water at about 200 F. in said eluent to generate therein liquid water, immediately neutralizing said thus-cooled eluent, by admixing with said etluent as liquid water is generated therein, said neutralizing agent.

References Cited in the le of this patent UNITED STATES PATENTS 1,569,532 Berry Ian. 12, 1926 2,487,576 Meyers Nov. 8, 1949 2,499,435 Whitacre Mar. 7, 1950 2,621,216 White Dec. 9, 1952 

1. A METHOD FOR SUBSTANTIALLY ELIMINATING CORROSION OF EQUIPMENT USED TO PROCESS AN EFFUENT STREAM WHICH, AS PRODUCED, IS ABOVE THE DEW POINT OF WATER IN THE EQUIPMENT UNDER THE CONDITIONS PREVAILING UPON ITS PRODUCTION AND WHICH CONTAINS ACID GENERATING OR ACIDIC MATERIAL, WHICH IN CONTACT WITH LIQUID WATER, CAUSES CORROSION OF APPARATUS CONTAINING THE EFFLUENT STREAM AND WHICH EFFLUENT STREAM IS NEUTRALIZED IN ENSUING TREATMENT AND WHEREIN THE NEUTRALIZING AGENT WILL BE CRYSTALLIZED AND UNDESIRABLY PLUG EQUIPMENT UNLESS NEUTRALIZATION IS EFFECTED AT A TEMPERATURE AT OR BELOW THE DEW POINT OF WATER, THE STEPS WHICH COMPRISE MAINTAINING SAID EFFLUENT STREAM ABOVE THE DEW POINT OF WATER IN THE EQUIPMENT UNDER THE CON- 